Product for improving the quality of cast iron and for the manufacture of ferromanganese



Patented Sept. 13, 1938 e 2,130,228

PRODUCT FOR IMPROVING THE QUALITY OF CAST IRON AND FOR THE MANUFAC- TURE OF FER-ROMANGANESE Henry R. Clarke, Chattanooga, Tenn.

No Drawing. Application March 16,-1936, 5

Serlal'No. 69,164

5 Claims. (01. 75-3) My invention relates to amethod for improving content of the iron will not be reduced. Manthe quality of cast iron and pig iron, and particuganese ores containing manganous salts ,are not larly for reducing the sulphur content of both; available in quantities and are accordingly high and wherein the quality of pig iron is improved in price. The more prevalent manganese ores,

5 by auxiliary reduction of one of the ores someand consequently those most widely used, are times used as a part of a blast furnace burden. those in which the manganese is in the form of One of the object of my invention is to provide, manganese dioxide.

in the reducing of iron ore in a blast furnace, a I have noted that pig iron containing defects method in which the manganese ores sometimes commonly called graphite pockets is consistemployed in the furnacing operation are reduced ently produced in blast furnaces in which manin process from the dioxide to the monoxide form, ganese ore composed largely of the higher oxides or to the metallic state, before contacting with of manganese is employed in the furnacing operthe slag in the furnace. ation. On analyzing the material found in the A still further object of my invention is to so-called graphite pockets, I found it to be provide auxiliary means for reducing manganese magnetic in character, very hard, and to con- 15 ore to the metallic state in a blast furnace or tain a considerable percentage of manganese but cupola. practically no carbon. Pig iron containing such Another object of my invention is to provide a pockets makes inferior castings, having undemethod for reducing high oxides of manganese sirable surface conditions, a quality which does (such'as manganese dioxide), when such oxides not properly take an enamel coating; and further are used in blast furnaces for increasing the that such castings were often warped, being of a, manganese content of pig iron, to either or both different shape than that of the pattern. manganous oxide or metallic manganese in such I have also observed that cast iron melted a manner as to avoid undue loss of manganese under slag, a constituent of which was manganese in the slag. ore made up largely of the higher oxides of man- A further object of my invention is to provide ganese, contained cavities apparently identical in a method of refining cast iron by u e of fiuxing nature with the so-called graphite pockets in materials which include as an active ingredient pig iron. manganese in the form of manganous oxide. In my investigation of means to overcome the A still further object of my invention is to foregoing defects, as well as to reduce the sul- 30 provide, in the reducing of iron ore in a blast phur content of iron, I have discovered that the furnace, or the refining of pig iron in a cupola. higher oxides of manganese may be reduced to a method in which a slag is formed in process manganous oxide by heating them in intimate which shall contain manganese as an active inassociation with carbonaceous material. I have gredient in the form of manganous oxide. brought about such a reduction by forming a A still further object of my invention is to proslag, preferably basic in character, the initial convide a prepared slag for use in reducing iron ore stituents of the slag containing manganese diin a blast furnace or in refining iron in a cupola, oxide in finely divided form, in intimate associawhich shall contain manganese as an active tion with the carbonaceous material.

40 ingredient in the form of manganous oxide or The carbonaceous material is preferably one 40 metallic manganese. rich in hydrogen, such as powdered coal, saw- A still further object of my invention is to dust, tar or similar bituminous substance, mo- 7 provide a method of producing afiux adapted to -888 fl Starch, Sugar. any other fi ely be added to a furnace or cupola charge, which divided or liquid carbonaceous substance. Where flux when fused shall contain as an active inore is-reduced, or iron is melted under such a gredient manganese in the form of manganous slag, t Should e of a Superior q y, i-

oxide, form grain structure, and free from defects such It is known in the art that if manganese ore as have been hereinbefore enumerated. containing manganous salts is added to the I have further observed that manganese ore charge in a cupola. it has the property of reducing containing large percentages (around 60%) of the sulphur content of the iron, the sulphur conmanganese dioxide, melts at a relatively low temtent having been reduced in this manner from perature (about 2500 F.), forming a syrup-like .07% to .007%. It has also been observed that slag which does not attack acid materials such it the manganese ore employed in the cupola is as fire clay. I have also observed that said manin the form of manganwe dioxide, the sulphur ganese ore slag will not adhere to coke, their rela- 55 .or cupola operations.

tlonship being somewhat like the relationship between oil-covered solid matter and water.

It could not be expected that oxides incorporated in slag with the above properties would be readily reduced either by the reducing gases in a blast furnace or by direct contact with coke. It however would be expected that such a slag (being acid in character) would be readily absorbed by basic blast furnace slag and become an integral part of the latter slag. Thus the introduction into a blast furnace of high oxides of manganese without auxiliary means of reducing said oxides, would be expected to result in manganese being expelled from the blast furnace as a constituent of the slag rather than as an alloy of the iron or as ferro-manganese.

I have further observed that if coal or other carbonaceous matter rich in hydrogen is intimately mixed with manganese ore containing manganese dioxide, a large percentage of the manganese in the ore is reduced to metallic manganese when the mixture is brought to a temperature of about 2650 F.

Upon heating coal or other carbonaceous substances rich in hydrogen, such as hereinbefore enumerated, with manganese ore containing manganese principally in the form of manganese dioxide, I have noted that, contrary to its action with coke, the ore, when fused, has a tendency to adhere to, or to wet the carbonaceous material, which facilitates the intimacy necessary for prompt and proper reduction of the ore when they are heated together. It also facilitates the forming or briquettes or sinter, as will hereinafter be pointed out.

The slag may be formed in process in the furnacing of iron ore or in the melting of iron, or it may be prepared separately and added to the furnace or cupola charge. If formed in process, the constituents are preferably charged into the furnace in cans or other suitable containers so as to maintain the constituents in intimate association until the desired reduction of the manganese ores has taken place.

The constituents may also be mixed and brought to a high temperature in order to form sinter or clinker for charging into the furnace or cupola, to be further reduced by the heat in the furnacing operation. Also the constituents may be melted in a furnace or cupola separate from the iron to produce a molten slag which may be solidified and used when convenient in furnace Also the constituents may be formed into briquettes by first mixing them with suitable binding materials, such as cement or sodium silicate, and then molding or pressing the materials into shapes and sizes suitable for charging into furnaces.

There is preferably mixed with the carbonaceous material and manganese ore some basic material, such as lime, dolomite, or soda ash, when the manganese ore contains siliceous matter sufficient to render the fused mixtures acid in character. I have found that slags acid in character are not so effective in overcoming the defects heretofore mentioned.

I have found that a mixture of finely divided manganese ore (20% to 60% MnOz) and powdered coal in the proportions of 80% manganese ore to 20% coal, when heated, form suitable sinter or clinker. These proportions may, of course, be varied considerably, and limestone, or other basic materials, may be added thereto. For example, a mixture of 70% manganese ore, 20% coal, and 10% limestone, may be employed as slag forming material for use in a blast furnace, Mixtures for use in a blast furnace should have a high fusion point so as not to be absorbed by the other slag in the furnace before coming in contact with the iron. This high fusion point is best attained by the addition of limestone, as above set forth.

An example of a mixture suitable for making a slag basic in character for use in a cupola is as follows:

Percent Manganese ore 50 Soda ash 1O Limestone 25 Fluor spar 5 Coal Slags may be produced from mixtures such as the foregoing by fusing in a furnace or cupola separately, and when drawn off from the furnace chilled in water to form relatively small fragments; or it may be run into molds to form briquettes of the desired size. This slag may be then employed as a part of a furnace or cupola charge.

For producing a slag of the desired character, other combinations .will readily suggest themselves to those skilled in the art, bearing in mind that the result sought, in accordance with this invention, is the reduction of the higher oxides of manganese to the manganous or metallic state in such a manner that the manganese shall be available, when needed, and that there should be suiiicient carbonaceous material maintained in intimate contact with the manganese dioxide content of the mixture until heated to a sufliciently high temperature to reduce the manganese dioxide to the manganous or metallic state. I have found that this requires a temperature of around 2500 F.

In furnacing operations, to reduce the sulphur content of the iron and improve its quality, from 20 to 60 pounds of my improved mixture is added to a furnace or cupola per ton of iron. In blast furnace operations, the amount employed would be greater and would vary according to the desired manganese content of the iron. In some cases it might be found that the iron ore contains sufllcient manganese to supply the manganese content of the iron. In such cases from 20 to 60 pounds of the fiux or slag would be added solely for the purpose of reducing sulphur.

While I have described several ways of carrying out my invention, it will-be obvious to those skilled in the art that it is not so limited, but that various means and proportions will suggest themselves to those skilled in the art. I desire, therefore, that only such limitations shall be placed thereupon as are imposed by the prior art or as are specifically set forth in the appended claims.

What I claim is:

1. A material in the form of sinter or clinker for adding to'a blast furnace or cupola burden to improve the quality of the iron or to produce metallic manganese or ferro-manganese, comprising manganese ore containing manganese principally in the form of manganese dioxide, and carbonaceous material containing effective amounts of hydrocarbons, and possessing the property of adhering to the manganese ore during its reduction and in an amount sufficient to reduce the manganese ore.

2. A material for adding to a blast furnace or cupola burden to improve the quality of the iron or to produce metallic manganese or ferro-manganese comprising manganese ore containingmanganese principally in the form of manganese dioxide and hydrogenous carbonaceous material in an amount sufficient to reduce the manganese to a metallic state, and a binding agent, in the form of briquettes, said carbonaceous material having the property of being wet by, or of clinging to, molten slags or ores containing manganese.

3. A material for adding to a blast furnace or cupola charge to improve the quality of iron or to produc metallic manganese or ferro-manganese comprising manganese ore containing manganese principally in the form of manganese dioxide and hydrogenous carbonaceous material in finely divided form and in suflicient quantity to reduce the manganese to a metallic state, and means for holding said components in intimate association until a reducing temperature has been attained, said carbonaceous material having the property of adhering to or being wet by the manganese ore.

4. A material for adding to a blastfurnace or cupola charge to improve the quality of the iron or to produce metallic manganese or ferro-manganese comprising finely divided manganese ore containing manganese principally in the form of manganese dioxide and a finely divided hydrogenous carbonaceous substance having the property of being wet by said ore when the latter is fused, and in suflicient quantity to reduce the manganese to a metallic state, and means for holding said substances in intimate association until a reducing temperature has been attained.

5. A mixture for adding to a blast furnace or cupola burden to produce a basic slag containing manganese in a manganous or metallic state when heated to a reducing temperature, comprising manganese ore containing manganese principally in the form of manganese dioxide, sufficient hydrogenous' carbonaceous material to reduce said ore, a basic material in sufficient quantity to render slag formed from said mixture basic in character, said carbonaceous material having the property of clinging to and remaining with the ore while the latter is in the process of changing from solid to the liquid state and is being reduced, and means to hold the components of the mixture in intimate relation until a reducing temperature has been attained.

HENRY R. CLARKE. 

